Synthesis of S2- and PF2O2-bridged dinuclear ruthenium(IV) complex obtained from the reaction of disulfide-bridged ruthenium(III) dimer complex with dioxygen and water

Reaction of [{Ru(CH3CN)(3)[P(OMe)(3)](2)}(2)(mu-S-2)](PF6)(3) with a mixture of acetylene and O-2 gave a novel ruthenium(IV) dimer complex [{Ru(IV)(PFO3)[P(OMe)(3)](2)}(2)(mu-S)(mu-PF2O2)(2)]. The newly formed bridging and terminal ligands PF2O2- and PFO32- are produced from the reaction of PF6- with trace amounts of H2O in the solvent. Although acetylene is not incorporated in the final product, it is necessary to accelerate the reaction. Ruthenium(IV) complexes with S2- ligand are rare and only two examples are previously known. The crystal of [{Ru(PFO3)[P(OMe)(3)](2)}(2)(mu-S)(mu-PF2O2)(2)] is monoclinic, space group P2(1)/n, a = 11.061(5), b = 20.764(4), c = 17.074(3) Angstrom, beta = 95.74(2)degrees, V = 3901(1) Angstrom(3), and Z = 4. The bridging PF2O2- ligand coordinates to Ru atoms with the two oxygen atoms, while the terminal PFO32- ligand coordinates to a Ru atom with one of the oxygen atoms. The molecular structure is confirmed by P-31 and (FNMR)-F-19 spectroscopy.